Under acidic conditions and at high ionic strength, the zinc cation is removed from its metal complex with 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS₄) thus leading to the diacid free porphyrin, that subsequently self-organize into J-aggregates. The kinetics of the demetallation step and the successive supramolecular assembly formation have been investigated as a function of pH and ionic strength (controlled by adding ZnSO₄). The demetallation kinetics obey to a rate law that is first order in [ZnTPPS₄] and second order in [H⁺], according to literature, with k₂ = 5.5 ± 0.4 M⁻² s⁻¹ at 298 K (IS = 0.6 M, ZnSO₄). The aggregation process has been modeled according to an autocatalytic growth, where after the formation of a starting seed containing m porphyrin units, the rate evolves as a power of time. A complete analysis of the extinction time traces at various wavelengths allows extraction of the relevant kinetic parameters, showing that a trimer or tetramer should be involved in the rate-determining step of the aggregation. The extinction spectra of the J-aggregates evidence quite broad bands, suggesting an electronic coupling mechanism different to the usual Frenkel exciton coupling. Resonance light scattering intensity in the aggregated samples increases with increasing both [H⁺] and [ZnSO₄]. Symmetry breaking occurs in these samples and the J-aggregates show circular dichroism spectra with unusual bands. The asymmetry g-factor decreases in its absolute value with increasing the catalytic rate k_c, nulling and eventually switching the Cotton effect from negative to positive. Some inferences on the role exerted by zinc cations on the kinetics and structural features of these nanostructures have been discussed.

The remarkable acceleration of Cu^II and Zn^II insertion in cationic porphyrins monodispersed on a polyglutamate anionic surface allows determination of the two metal ions down to nanomolar concentrations.

The interaction between gold sub-nanometer clusters composed of ten atoms (Au₁₀) and tetrakis(4-sulfonatophenyl)porphyrin (TPPS) was investigated through various spectroscopic techniques. Under mild acidic conditions, the formation, in aqueous solutions, of nanohybrid assemblies of porphyrin J-aggregates and Au₁₀ cluster nanoparticles was observed. This supramolecular system tends to spontaneously cover glass substrates with a co-deposit of gold nanoclusters and porphyrin nanoaggregates, which exhibit circular dichroism (CD) spectra reflecting the enantiomorphism of histidine used as capping and reducing agent. The morphology of nanohybrid assemblies onto a glass surface was revealed by atomic force microscopy (AFM), and showed the concomitant presence of gold nanoparticles with an average size of 130 nm and porphyrin J-aggregates with lengths spanning from 100 to 1000 nm. Surface-enhanced Raman scattering (SERS) was observed for the nanohybrid assemblies.

The hierarchical self-assembling kinetics of the porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TPPS₄⁴⁻) into J-aggregates at high ionic strength under acidic conditions and eventually in the presence of an added chiral templating agent (tartrate) were investigated through UV/Vis spectroscopy, resonance light scattering, and circular dichroism (CD). The effect of changing the mixing order of the various components in the solution on the kinetic parameters and the expression of chirality on the final J-aggregates was evaluated. In this latter case, only when the chiral tartrate anion is premixed with the porphyrin, the resulting nano-architectures exhibit CD spectra that reflect the handedness of the chiral inducer. We discuss a general mechanistic scheme, with the involvement of ion pairs or dimers that offer an alternative pathway to the aggregation process.